JP2006045284A - Manufacturing method of photocurable, oligomer chain-terminated (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing efficiently and easily a photocurable, oligomer chain-terminated (meth)acrylate which gives high crosslinking density without use of a tin compound as a catalyst. <P>SOLUTION: The manufacturing method of the photocurable, oligomer chain-terminated (meth)acrylate, which is represented by formula (II), comprises subjecting a lower alkyl (meth)acrylate and an alcohol terminated with an oligomer chain, which is represented by formula (I), to transesterification in the presence of an ester exchange catalyst and then treating the obtained reaction mixture with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent. In formula (I) A indicates an oligomer residue and n indicates 1 or 2. In formula (II) A and n are each as mentioned in the above and R<SP>1</SP>indicates a hydrogen atom or a methyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a photocurable oligomer chain terminal (meth) acrylate. More specifically, the present invention relates to a method for producing a photocurable rubber-based oligomer chain terminal (meth) acrylate useful for a sealing material for electronic materials, an adhesive and the like.

  As resins useful for adhesives and molding resins, rubber oligomers such as polybutadiene having a functional group such as a hydroxyl group or an acryloyl group at the end of the main chain of the oligomer are used. The rubber-based oligomer exhibits water resistance, chemical resistance, electrical characteristics and the like by being cured.

  As a method for curing a rubber-based oligomer, for example, a thermosetting method using a peroxide as a catalyst, a photocuring method of irradiating ultraviolet rays, and the like are known.

  However, the thermosetting method has an advantage that a resin having a high crosslinking density can be obtained, but has a disadvantage that the work for the curing is complicated. In addition, the photocuring method has an advantage of excellent workability, but has a disadvantage that the crosslinking density is insufficient.

  As a resin that eliminates these drawbacks, liquid polybutadiene (meth) acrylate in which a rubber oligomer and a (meth) acryloyl group are bonded by a urethane bond has been proposed (for example, see Patent Document 1).

However, when the liquid polybutadiene (meth) acrylate is produced, a tin compound is used as a catalyst, and the tin compound remains in the obtained liquid polybutadiene (meth) acrylate. ) The use of acrylate as an electronic material is not preferred in terms of corrosivity, reliability, and environment.
JP 2002-371101 A

  The present invention has been made in view of the above prior art, and provides a method for efficiently and easily producing a photocurable oligomer chain terminal (meth) acrylate that gives a high crosslinking density without using a tin compound as a catalyst. The task is to do.

  The present invention relates to a (meth) acrylic acid lower alkyl ester and the formula (I):

(In the formula, A represents an oligomer residue, and n represents 1 or 2)
Is subjected to a transesterification reaction in the presence of a transesterification catalyst, and the resulting reaction mixture is treated with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent. Formula (II) characterized by processing:

(In the formula, A and n are the same as above. R ¹ represents a hydrogen atom or a methyl group)
It relates to the manufacturing method of photocurable oligomer chain terminal (meth) acrylate represented by these.

  In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”.

  According to the production method of the present invention, it is possible to efficiently and easily produce a photocurable oligomer chain terminal (meth) acrylate that gives a high crosslinking density without using a tin compound as a catalyst.

  In the (meth) acrylic acid lower alkyl ester, the lower alkyl ester moiety preferably has 1 to 4 carbon atoms.

  Specific examples of the (meth) acrylic acid lower alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate and the like. Among these, methyl (meth) acrylate is preferable because it is inexpensive and has excellent versatility.

  The oligomer chain end alcohol has the formula (I):

(In the formula, A represents a diene oligomer chain, and n represents 1 or 2)
It is a compound represented by these.

  In the formula (I), typical examples of A include an oligomer chain obtained by polymerizing a conjugated diene and, if necessary, another copolymerizable monomer, or an oligomer chain obtained by hydrogenating the oligomer chain. .

  Examples of polymers constituting suitable diene oligomer chains include polyisoprene, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polychloroprene, poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol. , Poly- [epsilon] -caprolactone, and those obtained by hydrogenating them. Among these, polybutadiene that may be hydrogenated and polyisoprene that may be hydrogenated are more preferable.

  In the formula (I), n represents the number of hydroxyl groups bonded to the diene oligomer chain constituting the A. n is 1 or 2.

  There is no particular limitation on the method for producing the oligomer chain terminal alcohol represented by the formula (I). The oligomer chain terminal alcohol can be easily prepared by a known method, for example, by introducing a hydroxyl group with ethylene oxide or prolenoxide into the polymer constituting the diene oligomer chain.

  The number average molecular weight of the oligomer chain terminal alcohol represented by the formula (I) is from 500 to 10,000, preferably from 1,000 to 10,000, more preferably from the viewpoint of enhancing photocurability and improving the handling property in a liquid state. It is desirable that it is 1000-8000, More preferably, it is 2000-8000.

  The transesterification reaction between the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol represented by the formula (I) is carried out in the presence of a transesterification catalyst.

  Preferable examples of the transesterification catalyst include titanium compounds such as tetraethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, tetramethoxy titanate, tetraethoxy titanate, titanium tetrachloride, titanium tetrabromide; lithium methylate, lithium ethyl Alkali metal alcoholates such as sulfate, sodium methylate, sodium ethylate; alkaline earth metal alcoholates such as calcium methylate, calcium ethylate, magnesium methylate, magnesium ethylate; aluminum alcoholates such as aluminum methylate, aluminum ethylate; Examples thereof include lithium hydroxide; boron halides such as boron trifluoride, boron trichloride, boron tribromide, and the like. It can be mixed and used. Among the transesterification catalysts, a titanium compound and lithium hydroxide are preferable from the viewpoint of allowing the transesterification reaction to proceed efficiently.

  The amount of the transesterification catalyst is desirably 0.00001 mol or more, preferably 0.0001 mol or more, per mol of the oligomer chain terminal alcohol from the viewpoint of efficiently proceeding the transesterification reaction, and reducing the production cost. From the viewpoint of improving yield, reducing waste, and suppressing polymerization of the lower alkyl ester of (meth) acrylic acid, it should be 0.1 mol or less, preferably 0.03 mol or less per mol of oligomer chain terminal alcohol. desirable. From these viewpoints, the amount of the transesterification catalyst is 0.00001 to 0.1 mol, preferably 0.0001 to 0.03 mol, per mol of oligomer chain terminal alcohol.

  The transesterification reaction between the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol can be carried out in the presence or absence of a solvent.

  Examples of the solvent that can be used in the transesterification reaction include aliphatic hydrocarbon compounds such as n-hexane, heptane, and octane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; benzene, toluene , Xylene, cumene and other aromatic hydrocarbon compounds; tetrahydrofuran, di-n-butyl ether, ethylene glycol dimethyl ether, and ether solvents such as ethylene glycol diethyl ether, and the like, but the present invention is limited to such examples only. Is not to be done. Of these solvents, n-hexane is preferred.

  The amount of the solvent is not particularly limited, but is usually preferably 0 to 500 parts by weight, more preferably 0 to 100 parts by weight with respect to 100 parts by weight of the oligomer chain terminal alcohol.

  From the viewpoint of suppressing the polymerization of the (meth) acrylic acid lower alkyl ester, when the transesterification of the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol represented by the formula (I) is carried out, It is preferable to stir in an air stream or use a polymerization inhibitor.

  Specific examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4 -Benzooxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2, 2,6,6-tetramethylpiperidine N-oxy radical compounds such as —N-oxyl; hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol) ) 2,6-di-t-butyl-N, N-dimethylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4-t-butylcate Phenolic compounds such as 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol); phenothiazine, Amino such as N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine Compound; Hydroxylamine compounds such as 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 4-dihydroxy-2,2,6,6-tetramethylpiperidine; benzoquinone, 2,5-di- quinone compounds such as t-butylhydroquinone; copper compounds such as cuprous chloride and copper dimethyldithiocarbamate These may be used alone or in admixture of two or more thereof.

  Among the polymerization inhibitors, not only (meth) acrylic acid lower alkyl esters but also the polymerization of the photocurable oligomer chain terminal (meth) acrylate as the target compound can be effectively suppressed. A radical compound, a phenol compound, an amino compound, and a hydroxylamine compound are preferable, and these may be used alone or in combination of two or more. Among these, from the viewpoint of effectively suppressing polymerization of (meth) acrylic acid lower alkyl ester and photocurable oligomer chain terminal (meth) acrylate, N-oxy radical compound or N-oxy radical compound and The combined use with a phenol compound is more preferable.

  In addition, the said polymerization inhibitor can also be used together with another polymerization inhibitor. Thus, when the said polymerization inhibitor and another polymerization inhibitor are used together, the more superior polymerization inhibitory effect may be expectable by the synergistic effect by both combined use.

  The amount of the polymerization inhibitor is from 5 to 5000 ppm of the (meth) acrylic acid lower alkyl ester, preferably from the viewpoint of sufficiently exhibiting the polymerization inhibitory effect and obtaining the photocurable oligomer chain terminal (meth) acrylate in a high yield. It is desirable that it is 50-3000 ppm.

  Although the reaction temperature in the transesterification reaction is not particularly limited, it is usually about 60 to 150 ° C., preferably the reflux temperature. In addition, the reaction atmosphere during the transesterification reaction is preferably a gas containing air, oxygen gas or oxygen gas from the viewpoint of suppressing polymerization of the (meth) acrylic acid lower alkyl ester. More preferably.

  In the transesterification reaction, lower alcohol is by-produced as the transesterification proceeds. The by-produced lower alcohol is preferably removed from the reaction system as an azeotropic mixture with (meth) acrylic acid lower alkyl ester or reaction solvent.

  The end point of the transesterification reaction can be easily confirmed by the fact that the azeotropic mixture is no longer distilled. When the end point of the transesterification reaction is confirmed in more detail, it can be easily confirmed, for example, by introducing a protecting group having ultraviolet absorptivity into the residual hydroxyl group of the reaction mixture by high performance liquid chromatography or the like. .

  Since the reaction time of the transesterification reaction varies depending on the reaction conditions and the like, it cannot generally be determined, but is usually about 5 to 30 hours.

  A reaction mixture containing the photocurable oligomer chain end (meth) acrylate is thus obtained. In order to increase the purity of the photocurable oligomer chain end (meth) acrylate, the reaction mixture may be concentrated.

  Next, the obtained reaction mixture is treated with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent.

  When the reaction mixture is treated with the solid adsorbent, the catalyst contained in the reaction mixture is removed by the solid adsorbent, so that the purity of the photocurable oligomer chain terminal (meth) acrylate can be increased.

  Examples of the solid adsorbent include activated clay, activated carbon, silica gel, acidic ion exchange resin, hydrotalcite and the like, and these can be used alone or in admixture of two or more. Among these, the combined use of silica gel and hydrotalcite and the combined use of acidic ion exchange resin and hydrotalcite are preferable because they have an excellent catalyst removal effect.

  If the transesterification catalyst used in the transesterification reaction is an alkyl titanate such as tetraethyl titanate, tetraisopropyl titanate or tetra n-butyl titanate, or an alkoxy titanate such as tetramethoxy titanate or tetraethoxy titanate, the reaction mixture contains By adding water, the catalyst removal efficiency by the solid adsorbent can be increased. In this case, the amount of water is 0.1% relative to 100 parts by weight of the reaction mixture from the viewpoint of increasing the catalyst removal efficiency and suppressing the hydrolysis of the generated photocurable oligomer chain terminal (meth) acrylate. It is desirable that the amount is from 05 to 20 parts by weight, preferably from 0.1 to 10 parts by weight.

  The amount of the solid adsorbent is 0.01 to 10 per 100 parts by weight of the photocurable oligomer chain end (meth) acrylate contained in the reaction mixture in consideration of the adsorptivity of the catalyst and the filterability of the adsorbent thereafter. Part by weight, preferably 0.05 to 5 parts by weight is desirable.

  A mixed solvent of a hydrophilic solvent and a lipophilic solvent exhibits an effect of increasing the contact efficiency between the catalyst contained in the photocurable oligomer chain terminal (meth) acrylate and water.

  The hydrophilic solvent referred to in this specification means an organic solvent having a solubility in 100 parts by weight of water at 25 ° C. of 8 parts by weight or more. Moreover, the lipophilic solvent as used in this specification means the organic solvent which can melt | dissolve an oligomer chain terminal alcohol and an oligomer chain terminal (meth) acrylate.

  Examples of the hydrophilic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; and C1 to C4 such as methanol, ethanol, propanol, butanol, ethylene glycol and glycerin. These may be used alone or in combination of two or more. Of these, acetone and tetrahydrofuran are preferred.

  Examples of the lipophilic solvent include aliphatic hydrocarbon compounds such as n-hexane, heptane, and octane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatics such as benzene, toluene, xylene, and cumene. Examples thereof include hydrocarbon compounds; ethers such as di-n-butyl ether; oil-soluble alcohols having 5 to 12 carbon atoms, and these can be used alone or in admixture of two or more. Of these, n-hexane and toluene are preferred.

  Suitable hydrophilic and lipophilic solvent combinations include, for example, a combination of acetone and toluene, a combination of methyl ethyl ketone and toluene, and a combination of tetrahydrofuran and toluene.

  The weight ratio of the hydrophilic solvent to the lipophilic solvent (hydrophilic solvent / lipophilic solvent) is 1/99 to 30 from the viewpoint of increasing the solubility of the oligomer chain terminal (meth) acrylate and the solubility of water in the solvent. / 70, preferably 3/97 to 10/90.

  The amount of the mixed solvent of the hydrophilic solvent and the lipophilic solvent is determined based on the oligomer chain end from the viewpoint of reducing the viscosity of the generated oligomer chain end (meth) acrylate and increasing the contact efficiency between the remaining catalyst and water. The amount is 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight per 100 parts by weight of alcohol.

  The adsorption removal of the catalyst contained in the reaction mixture by the solid adsorbent can be performed, for example, by adding the solid adsorbent and the mixed solvent to the reaction mixture and then stirring.

  From the viewpoint of the operability and the thermal stability of the photocurable oligomer chain terminal (meth) acrylate, the treatment temperature during the adsorption removal of the catalyst is preferably 20 to 150 ° C., preferably 50 to 100 ° C. . The treatment time is not particularly limited, but is usually about 1 to 30 hours, preferably about 3 to 10 hours.

  Thus, after performing the adsorption treatment, the solid adsorbent and impurities contained in the mixture are removed by filtration.

  For the filtration, for example, pressure filtration, vacuum filtration, centrifugal filtration, or the like can be used. In that case, in order to prevent the load by filtration, you may use diatomaceous earth as a filter aid.

  After filtration, by concentrating the obtained filtrate, impurities such as a decomposition product of the transesterification catalyst are distilled off, and the purity of the photocurable oligomer chain terminal (meth) acrylate can be further increased.

  Thus, formula (II):

(In the formula, A and n are the same as above. R ¹ represents a hydrogen atom or a methyl group)
The photocurable oligomer chain terminal (meth) acrylate represented by can be easily and efficiently obtained.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Example 1
In a 10 L reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 2742 g of hydrogenated polybutadiene alcohol at both ends (number average molecular weight 5500), 379 g of methyl acrylate, 380 g of n-hexane, 0.8194 g of hydroquinone monomethyl ether And 0.5533 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. While passing the obtained mixture through a calcium chloride tube, air was blown into the mixture, and reflux dehydration was performed at 80 to 85 ° C.

  Moisture contained in the mixture was measured by the Karl Fischer method, and after confirming that the water content was 200 ppm or less, as a transesterification catalyst, 1.36885 g of tetra n-butyl titanate was added to the mixture, While the produced methanol was distilled out of the reaction system under reflux of n-hexane, which is an azeotropic solvent, the reaction was performed at a reaction temperature of 80 to 85 ° C. for 10 hours with stirring.

  After completion of the reaction, the conversion rate of the hydrogenated polybutadiene diterminated diacrylate in the reaction mixture was determined by high performance liquid chromatography (HPLC) to be 99.2%.

  Next, the temperature in the reaction vessel is adjusted to 75 to 80 ° C., and concentrated at a reduced pressure of 70 to 2 kPa until 95% or more of the used methyl acrylate and n-hexane are distilled off. n-Hexane was recovered.

To 2070 g of the obtained hydrogenated polybutadiene diterminated diacrylate, 2000 g of toluene, 200 g of acetone, 20 g of ion-exchanged water, and hydrotalcite (composition formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) [ 20 g of Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 500PL] was added and treated at 75-80 ° C. for 2 hours.

  Next, by adjusting the temperature in the reaction vessel to 75 to 80 ° C. and concentrating at a reduced pressure of 90 to 35 kPa, 400 g of a mixed distillate of toluene, acetone and water was recovered to obtain a concentrated solution.

  The obtained concentrated solution is filtered under air pressure to separate the catalyst and the adsorbent, and the obtained filtrate is concentrated at a temperature of 60 to 80 ° C. at a reduced pressure of 30 to 0.8 kPa. A liquid was obtained and toluene was collected.

  This concentrated liquid contains hydrogenated polybutadiene both terminal diacrylate as a photocurable oligomer chain terminal (meth) acrylate, and its property is a pale yellow viscous liquid, the conversion is 99.4%, The hue (hereinafter referred to as APHA) was 80, and the residual catalyst amount was 50 ppb or less.

  In each example, the conversion rate, hue, and residual catalyst amount of the photocurable oligomer chain terminal (meth) acrylate produced were measured based on the following methods.

(1) Conversion 0.1 g of the reaction mixture after completion of the reaction was diluted with 20 mL of n-hexane, 0.3 g of p-nitrobenzoyl chloride and 0.5 g of pyridine were added to the resulting diluted solution, and the mixture was sealed in a sealed state. After making it react at 10 degreeC for 10 minutes, 10 g of water was added and stirred. After standing, the supernatant was analyzed by liquid chromatography (hereinafter referred to as LC), and the formula:
[Conversion rate (%)]
= [1- (Alcohol LC area at the end of reaction ÷ Alcohol LC area at the start of reaction)]
× (Sample weight at the start of reaction ÷ Sample weight at the end of reaction)] × 100
Based on the above, the conversion rate was obtained.

(2) Hue (APHA)
The hue of the generated photocurable oligomer chain end (meth) acrylate is compared with the APHA standard color, and the closest standard color number in the standard color sequence is the hue of the photocurable oligomer chain end (meth) acrylate (APHA) ).

(3) Residual catalyst amount The residual catalyst amount is included in the photocurable oligomer chain terminal (meth) acrylate produced using inductively coupled plasma emission spectrometry (ICP-AES, manufactured by PerkinElmer, product number: Optima4300DV type). It was determined by quantifying the amount of catalyst present.

Example 2
In Example 1, 1200 g of hydrogenated polybutadiene one-end alcohol (number average molecular weight 6500), 154 g of methyl acrylate, 154 g of n-hexane, 0.3602 g of hydroquinone monomethyl ether and 4-hydroxy-2,2,6,6-tetramethyl Piperidine-N-oxyl (0.2413 g) was charged, refluxed and dehydrated at 80 to 85 ° C., 0.3643 g of tetra n-butyl titanate was added, and the resulting methanol was removed and stirred at a temperature of 80 to 85 ° C. while stirring. The reaction was performed in the same manner as in Example 1 except that the reaction was performed for a period of time.

  After completion of the reaction, the conversion rate of the hydrogenated polybutadiene one-end monoacrylate in the reaction mixture was determined by HPLC and found to be 99.1%.

  Next, the temperature in the reaction vessel was adjusted to 75 to 80 ° C., and concentrated at a reduced pressure of 70 to 2 kPa to recover excess methyl acrylate and n-hexane.

1204 g of toluene, 60 g of acetone and 12 g of ion-exchanged water are added to 1220 g of the resulting hydrogenated polybutadiene one-end monoacrylate, treated at 75-80 ° C. for 10 hours, and then the temperature in the system is adjusted to 75-80 ° C. Then, the mixture was concentrated at a reduced pressure of 90 to 35 kPa, and 120 g of a mixed distillate of toluene, acetone and water was recovered. Then, 4.8 g of hydrotalcite (compositional formula Al ₂ O ₃ .9SiO ₂ .H ₂ O) [Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 700] is added as a transesterification catalyst, and 75-80 Treated for 1 hour at ° C.

  This treatment solution was filtered using 15 g of diatomaceous earth (trade name: Radiolite # 700, manufactured by Kyowa Chemical Industry Co., Ltd.) as a filter aid under air pressure to separate the catalyst and the adsorbent, The temperature inside was adjusted to 60 to 80 ° C., and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained hydrogenated polybutadiene one-end monoacrylate was a pale yellow viscous liquid, the conversion was 99.1%, and APHA was 30.

Example 3
In Example 2, 154 g of methyl acrylate was changed to 248 g of methyl methacrylate, and the same operation as in Example 2 was performed, except that the amount of hydrogenated polybutadiene one-end alcohol (number average molecular weight 6500) was changed to 1094 g. .

  After completion of the reaction, the conversion rate of the hydrogenated polybutadiene one-end monomethacrylate in the reaction mixture was determined by HPLC and found to be 98.1%.

  Next, the temperature in the system was adjusted to 75 to 80 ° C., and concentrated at a reduced pressure of 70 to 2 kPa to recover excess methyl acrylate and n-hexane.

  To 1110 g of the obtained hydrogenated polybutadiene one-end monomethacrylate, 1094 g of toluene, 55 g of acetone and 11 g of ion-exchanged water were added and treated at 75 to 80 ° C. for 10 hours.

Next, the temperature in the system was adjusted to 75 to 80 ° C. and concentrated at a reduced pressure of 60 to 25 kPa, and 110 g of a toluene, acetone and water mixed distillate was recovered. Thereafter, 2.2 g of hydrotalcite (compositional formula Al ₂ O ₃ .9SiO ₂ .H ₂ O) [manufactured by Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 700] was added as a transesterification catalyst, and 75-80 Treated for 2 hours at a temperature of ° C.

  This treatment liquid was filtered using 7 g of diatomaceous earth (trade name: Radiolite # 700, manufactured by Kyowa Chemical Industry Co., Ltd.) as a filter aid under air pressure to separate the catalyst and the adsorbent, The temperature inside was adjusted to 60 to 80 ° C., and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained hydrogenated polybutadiene one-end monomethacrylate is a pale yellow viscous liquid, the conversion is 97.3%, APHA is 30, and the amount of residual transesterification catalyst is determined by inductively coupled plasma emission spectrometry (ICP-AES: It was 67 ppb when quantified with Perkin Elmer, Optima 4300 DV type).

Example 4
In Example 1, 220 g of hydrogenated polybutadiene both-end alcohol (number average molecular weight 4000, molar ratio of 1,2-adduct to 1,4-adduct: 9/1), 83.5 g of methyl acrylate, n- Charge 83.2 g of hexane, 0.0634 g of hydroquinone monomethyl ether and 0.0389 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and after refluxing dehydration at 75-80 ° C., tetra n-butyl The same operation as in Example 1 was performed except that 0.2645 g of titanate was added and the reaction was performed at 75 to 80 ° C. for 8 hours while removing the generated methanol and stirring.

  After the completion of the reaction, the conversion rate of hydrogenated polybutadiene diterminated diacrylates in the reaction mixture was determined by HPLC and found to be 98.4%.

  Next, the temperature in the system was adjusted to 70 to 75 ° C., and concentrated at a reduced pressure of 70 to 2 kPa to recover excess methyl acrylate and n-hexane.

  To 225 g of the obtained hydrogenated polybutadiene diterminated diacrylate, 215 g of toluene, 10 g of acetone and 2.1 g of ion-exchanged water were added and treated at 75-80 ° C. for 10 hours.

Next, the temperature in the system was adjusted to 70 to 75 ° C. and concentrated at a reduced pressure of 90 to 35 kPa, and 20 g of a mixed distillate of toluene, acetone and water was recovered. Thereafter, hydrotalcite (formula _{Al 2 O 3 · 9SiO 2 ·} H 2 O) [manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyoward 700] was added 2g, were treated for 3 hours at 75-80 ° C. .

  This treatment solution was filtered using 6 g of diatomaceous earth (trade name: Radiolite # 700, manufactured by Kyowa Chemical Industry Co., Ltd.) as a filter aid under air pressure to separate the catalyst and the adsorbent, The temperature inside was adjusted to 60 to 70 ° C., and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained hydrogenated polybutadiene diterminal diacrylate was a pale yellow viscous liquid, the conversion was 96.5%, and APHA was 30.

Example 5
In Example 4, 222 g of hydrogenated polybutadiene terminal alcohol (number average molecular weight 5000, molar ratio of 1,2-adduct to 1,4-adduct: 2/8), 60.5 g of methyl acrylate, n- 61.5 g of hexane, 0.0705 g of hydroquinone monomethyl ether and 0.0402 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl were charged, and after reflux dehydration at 75 to 80 ° C., tetra n-butyl The same operation as in Example 4 was performed except that 2.240 g of titanate was added and the reaction was performed at 75 to 80 ° C. for 8 hours while removing the generated methanol and stirring.

  After completion of the reaction, the temperature in the system was adjusted to 70 to 85 ° C. and concentrated at a reduced pressure of 70 to 2 kPa to recover excess methyl acrylate and n-hexane.

To 22.5 g of the obtained hydrogenated polybutadiene diterminated diacrylate, 220 g of toluene, 11 g of acetone, 2.2 g of ion-exchanged water, weakly acidic cation exchange resin [manufactured by Organo Corporation, trade name: Amberlite IRC50] 40 g and Hydrotalcite (composition formula Mg _0.7 Al _0.3 O _1.15 ) [Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 2000] 40 g was added and treated at 75 to 80 ° C. for 2 hours.

  Next, the temperature in the system was adjusted to 70 to 75 ° C. and concentrated at a reduced pressure of 90 to 20 kPa, and 22 g of a mixed distillate of toluene, acetone and water was recovered.

  This concentrated solution was filtered under air pressure to separate the catalyst and the adsorbent, and then the temperature in the system was adjusted to 60 to 70 ° C. and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained hydrogenated polybutadiene diterminal diacrylate was a light yellow solid. In addition, since the obtained hydrogenated polybutadiene both terminal diacrylate was solid, its conversion rate and APHA could not be measured.

Example 6
In Example 5, 749 g of non-hydrogenated polybutadiene both terminal alcohols (number average molecular weight 5000, 1,2-adduct to 1,4-adduct molar ratio: 2/8) 749 g, methyl acrylate 188.5 g, n -127 g of hexane, 0.2176 g of hydroquinone monomethyl ether and 0.1540 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl were added, refluxed and dehydrated at 75 to 80 ° C., and then tetra-n-butyl titanate The same operation as in Example 5 was performed except that 7.50 g was added and the reaction was performed at 75 to 80 ° C. for 10 hours while removing the generated methanol and stirring.

  After completion of the reaction, the conversion rate of the hydrogenated polybutadiene diterminal diacrylate in the reaction mixture was determined by HPLC and found to be 95.8%.

  Next, the temperature in the system was adjusted to 70 to 75 ° C., and concentrated at a reduced pressure of 70 to 2 kPa to recover excess methyl acrylate and n-hexane.

To 760 g of the obtained non-hydrogenated polybutadiene diterminated diacrylate, 750 g of toluene, 38 g of acetone, 7.5 g of ion-exchanged water, 75 g of weak acid cation exchange resin [manufactured by Organo Corporation, trade name: Amberlite IRC50] and hydro 150 g of talcite (compositional formula Mg _0.7 Al _0.3 O _1.15 ) [Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 2000] was added and treated at 75-80 ° C. for 2 hours.

  Next, the temperature in the system was adjusted to 70 to 75 ° C. and concentrated at a reduced pressure of 90 to 20 kPa, and 80 g of a mixed distillate of toluene, acetone and water was recovered.

  This concentrated solution was filtered under air pressure to separate the catalyst and the adsorbent, and then the temperature in the system was adjusted to 60 to 70 ° C. and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained non-hydrogenated polybutadiene diterminated diacrylate was a pale yellow viscous liquid, the conversion was 87.0%, and the APHA was 120.

Example 7
In Example 6, 400 g of non-hydrogenated polybutadiene both terminal alcohols [number average molecular weight 5000, molar ratio of 1,2-adduct to 1,4-adduct: 2/8], 112 g of methyl acrylate, n-hexane 200 g, 0.1242 g of hydroquinone monomethyl ether and 0.083 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl were charged, and after reflux dehydration at a temperature of 75 to 80 ° C., lithium hydroxide 4. The same operation as in Example 6 was performed, except that 0 g was added and the reaction was performed at 75 to 80 ° C. for 10 hours while removing the generated methanol and stirring.

After completion of the reaction, 35.6 g of hydrotalcite (compositional formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) [Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 500PL] was added, and 75 ~ Treated at 80 ° C. for 2 hours.

  This treatment liquid is filtered under air pressure to separate the catalyst and the adsorbent, and then the temperature in the system is adjusted to 70 to 75 ° C., concentrated at a reduced pressure of 70 to 0.8 kPa, and excess methyl acrylate and n-Hexane was recovered.

  The obtained non-hydrogenated polybutadiene diterminated diacrylate was a pale yellow viscous liquid, the conversion was 97.0%, and the APHA was 200.

Example 8
In Example 1, 222 g of hydrogenated isoprene-terminated alcohol (number average molecular weight 2700) 222 g, methyl acrylate 59.4 g, n-hexane 61.0 g, hydroquinone monomethyl ether 0.0703 g and 4-hydroxy-2,2,6, 0.0410 g of 6-tetramethylpiperidine-N-oxyl was charged, refluxed and dehydrated at 75 to 80 ° C., 4.4 g of tetra n-butyl titanate was added, and the resulting methanol was removed and stirred at 75 to 80 ° C. The same operation as in Example 1 was performed except that the reaction was performed for 8 hours.

  After completion of the reaction, the conversion rate of the hydrogenated isoprene-terminated diacrylate in the reaction mixture was determined by HPLC and found to be 99.3%.

  Next, the temperature in the system was adjusted to 70 to 80 ° C. and concentrated at a reduced pressure of 60 to 2 kPa, and excess methyl acrylate and n-hexane were recovered.

  222 g of toluene, 11 g of acetone and 4.4 g of ion-exchanged water are added to 225 g of the resulting hydrogenated isoprene-terminated diacrylate, and the mixture is treated at 75-80 ° C. for 10 hours, and then the temperature in the system is increased to 70-75 ° C. The mixture was adjusted and concentrated at a reduced pressure of 90 to 35 kPa, and 20 g of a mixed distillate of toluene, acetone and water was recovered.

Next, hydrotalcite (formula _{Al 2 O 3 · 9SiO 2 ·} H 2 O) [manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyoward 700] was added 2 g, 3 hours at 75-80 ° C. did.

  This treatment solution was filtered using 6 g of diatomaceous earth (trade name: Radiolite # 700, manufactured by Kyowa Chemical Industry Co., Ltd.) as a filter aid under air pressure to separate the catalyst and the adsorbent, The temperature inside was adjusted to 60 to 70 ° C., and concentrated at a reduced pressure of 30 to 0.8 kPa to recover toluene.

  The obtained hydrogenated polybutadiene diterminated diacrylate was a pale yellow viscous liquid, the conversion was 87.1%, and APHA was 30.

Example 9
In Example 1, hydrogenated polybutadiene diterminated diacrylate was prepared in the same manner as in Example 1 except that 2000 g of toluene and 200 g of tetrahydrofuran were used instead of 2000 g of toluene and 200 g of acetone.

  The obtained hydrogenated polybutadiene diterminated diacrylate was a pale yellow viscous liquid, the conversion was 99.4%, and APHA was 100.

Example 10
In Example 1, hydrogenated polybutadiene diterminated diacrylate was prepared in the same manner as in Example 1 except that 2000 g of toluene and 200 g of methyl ethyl ketone were used instead of 2000 g of toluene and 200 g of acetone.

  The obtained hydrogenated polybutadiene both terminal diacrylate was a pale yellow viscous liquid, the conversion was 99.4%, and APHA was 120.

  From the above results, it can be seen that according to each Example, a photocurable rubber-based oligomer chain terminal (meth) acrylate having high purity can be efficiently produced on an industrial scale.

Comparative Example 1
In Example 1, hydrogenated polybutadiene diterminated diacrylate was prepared in the same manner as in Example 1 except that 2200 g of toluene was used instead of 2000 g of toluene and 200 g of acetone. As a result, the external appearance remained red, and the APHA was 500 or more.

Comparative Example 2
In Example 1, hydrogenated polybutadiene diterminated diacrylate was prepared in the same manner as in Example 1 except that 2200 g of acetone was used instead of 2000 g of toluene and 200 g of acetone. As a result, hydrogenated polybutadiene was not compatible and two-layer separation occurred. The appearance remained red and unchanged, and APHA was 500 or more.

  From the results of each comparative example, when a hydrophilic solvent or a lipophilic solvent was used alone, the contact efficiency and solubility of the oligomer chain terminal (meth) acrylate and water were insufficient as compared with each example. I know that there is.

  The photocurable oligomer obtained by the production method of the present invention can be used as, for example, a sealing material for electronic materials, an adhesive, and the like.

Claims (8)

(Meth) acrylic acid lower alkyl ester and formula (I):

(In the formula, A represents a diene oligomer chain, and n represents 1 or 2)
Is subjected to a transesterification reaction in the presence of a transesterification catalyst, and the resulting reaction mixture is treated with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent. Formula (II) characterized by processing:

(In the formula, A and n are the same as above. R ¹ represents a hydrogen atom or a methyl group)
The manufacturing method of the photocurable oligomer chain terminal (meth) acrylate represented by these.   The process according to claim 1, wherein A in formula (I) is a polybutadiene residue which may be hydrogenated or a polyisoprene residue which may be hydrogenated.   The production method according to claim 1 or 2, wherein the number average molecular weight of the oligomer chain terminal alcohol represented by the formula (I) is 500 to 10,000.   The production according to any one of claims 1 to 3, wherein the transesterification catalyst is at least one selected from the group consisting of titanium compounds, alkali metal alcoholates, alkaline earth metal alcoholates, aluminum alcoholates, lithium hydroxide, and boron halides. Law.   The production method according to any one of claims 1 to 4, wherein the amount of the transesterification catalyst is 0.00001 to 0.1 mol per mol of the compound represented by the formula (I).   A group consisting of an N-oxy radical compound, a phenol compound, an amino compound, and a hydroxylamine compound when a transesterification reaction is performed between the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol represented by the formula (I) The production method according to claim 1, wherein at least one polymerization inhibitor selected from the above is used.   The production method according to any one of claims 1 to 6, wherein the solid adsorbent is at least one selected from the group consisting of activated clay, activated carbon, silica gel, acidic ion exchange resin and hydrotalcite.   The production method according to any one of claims 1 to 7, wherein the amount of the solid adsorbent is 0.01 to 10 parts by weight per 100 parts by weight of the produced photocurable oligomer chain terminal (meth) acrylate.